Arylated naphthylamin sulfonic acids and process of making same.



WILHELM- HAHNENKAMM, or 'SIL'NIJLINGEN area.

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AssIeNonpo FARBWERKE voam. EISEEER 't'ficiti's & RfiiT1NG,-0F 'HiioHsr-ou- THE-MAIN, GERMANY, A CORPORATION or GERMANY.

ARYLATED NAP'HtHYLAMIN screams A'oms am) rnoonss or MAKING s'AM'E.

No Drawing.

To all whom it may concern.

Be it known that I, WILHELM Hanna s KAMM, Ph. D;, chemist, a citizen of the Em pire of Germany, residing at Sindli'ngen,

near Hiichst-on-the-Main, Germany, have invented certain newand useful Improvements in Arylated Naphthylamin Sulfonic Acids and Processes of Making Same, of which the following is a specification.

I have found that the para diamins (1111-. der which term are to be comprised not only the mononuclear diamins such as paraphenylenediamin, but also the heteronuclear diamins, such asberizidin, etc.,) for in-- NH,Ar.NH.Ns wherein the group NH2ALNH stands for the residue of a p-diamin and Ns for the residue of a naphthylamin sulfonic acid;

are soluble in diluted alkalis, and yield,

when oxidized together with a p-aminophenol, indophenols Which give by sulfuration with alkali-polysulfid in presence of copper, valuable green sulfur dyestuffs of I extremely great fastness.

- on condensing agent (these agents to be The condensation is advantageously cf fected by fusing at a suitable temperaturethe components with or without the addition of an'indifi'erent solvent or suspending comprised under-the term di1uents.)

The following examples serve to illustrate my invention, but are not intended to limit the same:

Example}: 44.6 kg. of 1-naiphthylamin-8- sulfonic acid. are mixed with 55.2 kg.-of benzidin' and this mixture is heated in a suitable apparatus to about 200 C. for 10 Specification of Letters kiitnt.

Application med March 7, 191a. Serial its. ceases;

r teatea ass. is, was.

heat, with hydrochloric acid until a test with Congo-red shows a slightly acid re action, whereupon the condensation prodnot of l-naphthylamin-8-sulfonic acid and benzidin separates as a green insoluble body. For purifying the body, it is re-dissolved in sodium carbonate and precipitated with hydrochloric acid, at boiling heat, or it is transformed into its calcium salt. By the latter method it is possible to dissociate the condensation "product into I two different components which are both suitable for the manufacture of dyestuffs. If. the 1.2-naphthylai'ninsulfohic acid be substituted for the 1.7 (or 1.8) uaphthylaminsulfonic acid, an analogous product is obtained which can be easily separated from the benzidin by -means of hydrochloric acid and isolated with caustic soda lye or common salt so as to obtain the sodium salt. solves in water and reprecipitates in caustic soda lye. 'Whenusing naphthylamindisul fonic acids, the procedure is the same; thus there is obtained, for instance from the 1.4.8-naphthylamindisulfonic acid and benzidin, a sulfonic acid of a greenish coloration.

xar'nple II: A paste, prepared from 19.9 kg. of p p-diaminodiphenylamin, is inti mate'ly mixed with 22.3 kg. of l-naphthylamin-S-sulfcnic acid and 30 kg. of glycerin, and this mixture is heated for 10 hours to. 150 C; There are then added while stirring for one hour, 350 kg. of hydrochloric acid 1 :10 at 70-80", the mass is filtered 0d and after removing the excess of p-p-diaminodiphenylami'n by washing with boiling hydrochloric acid 1:10, it is washed with Water until there is no further acid reaction to Congo-red, whereupon the finely distributed product is separated by boiling with a solution of sodium carbonate. The condensation product is precipitated-from the boiling so lution of sodium carbonate by boiling hydrochloric acid 1:50. For further purifying the product, the procedure may be as indi cated in example I.

Example III: A- paste, prepared from 10.8 kg. of p-phenylenediamin, is intimately mixed with 22.3 kg. of l-naphthylamin-S- sulfonic acid and 30kg. of glycerin, and this mixture is heated for ten hours to 150? C. There are then added while stirring for one hour, .350 kg. of hydrochloric acid 1:10 at 7 080, the mass is filtered 011' and after It readily disno further acid reaction to Congo-red, A

whereuponthe finely-distributed product is separated by boiling with a solution of sodium carbonate. The condensation prodof sodium carbonate by boiling hydrochloric acid 1:50. In this way a naphthylated sulfonic acid is obtained which is almost insoluble in diluted hydrochloric acid and also in hotwater and can be separated thereby from the p-phenylenediamin and the 1:8

naphthyla min sulfonic acid. It has the general formula:

is soluble in diluted alkalis, and yields, when oxidized together with p-amino-phenol, an indophenol which gives by sulfuration with alkalipolysulfid in presence of copper, valuable green sulfur dyestuffs of extremely great fastnss. Similar naphthylated'sulfonic acids are also produced by means of other diamins such as p-toluylenediamins. Besides water, there may be used the other usual diluents such, for instance, as glycerin, paraffin or the like.

Having now described my invention, what I claim, is:

1. The process of manufacturing new arylated naphthylamin sulfonic acids,which consists in condensing a para-diamin with a naphthylamin sulfonic acid.

2. The process of manufacturing new arylated naphthylamin sulfonic acids,which 3. As new articles of manufacture, the

products obtained by condensing a paradiamin with a naphthylamin sulfonic acid,

having the general formula; not is precipitated from the boiling solution NH Ar.NH.Ns

wherein the group NHTAIZNH stands for the residue of a p-diamin and Ns. for the residue of a naphthylamin sulfonic acid; said products'being soluble in diluted alkalis, yielding, when oxidized together with a. p-aminophenol, indophenols which give by sulfuration with alkali-polysulfids in presence of copper, valuable green sulfur dyestuffs 'of extremely great fastness.

4;. As anew article of manufacture, the product of the condensation of 1.8-naphthylamin sulfonic acid with p-phenylenediamin, being soluble in diluted alkalis and having the general formula: /NH: soa: and yielding, when oxidized together with p-amino-phenol, an indophenol which gives by sulfuration with alkalipolysulfid in presence of copper, valuable green sulfur dyestuffs of extremely great fastness.

In testimony whereof, I afiix my signature in presence of two witnesses.

DR. WILHELM HAHNENK'AMM.

Witnesses:

JEAN GR ND, CARL GRUND." 

